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The discrepancy between the trend in the diffusion coefficient of a lithium ion (D Li+ ) and that in the activation energy of ion hopping signals hidden factors determining ion transport kinetics in layered olivine phosphate materials (LiMPO4). Combining density functional theory (DFT) calculations and the Landau-Zener electron transfer theory, we unravel this hidden factor to be the electronic coupling between redox centers of the host materials. The ion transport process in LiMPO4 is newly described as an ion-coupled electron transfer (ET) reaction, where the electronic coupling effect on D Li+ is considered by incorporating the electronic transmission coefficient into the rate constant of the transfer reaction. The new model and DFT calculation results rationalize experimental values of D Li+ for various LiMPO4 (M = Fe, Mn, Co, Ni) materials, which cannot be understood solely by the calculated activation barrier of ion hopping. Interestingly, the electronic coupling between host redox centers is found to play an essential role. Particularly, the sluggish ion mobility in LiFePO4 is due to a very weak electronic coupling. The obtained insights imply that one can improve the rate performance of intercalation materials for metal-ion batteries through modifying the electronic coupling between redox centers of host materials.Glycosidases, which are the enzymes responsible for the removal of residual monosaccharides from glycoconjugates, are involved in many different biological and pathological events. The ability to detect sensitively the activity and spatiotemporal distribution of glycosidases in cells will provide useful tools for disease diagnosis. However, the currently developed fluorogenic probes for glycosidases are generally based on the glycosylation of the phenol group of a donor-acceptor type fluorogen. This molecular scaffold has potential drawbacks in terms of substrate scope, sensitivity because of aggregation-caused quenching (ACQ), and the inability for long-term cell tracking. Here, we developed glycoclusters characterized by aggregation-induced emission (AIE) properties as a general platform for the sensing of a variety of glycosidases. To overcome the low chemical reactivity associated with phenol glycosylation, here we developed an AIE-based scaffold, which is composed of tetraphenylethylene conjugated with dicyanomethylene-4H-pyran (TPE-DCM) with a red fluorescence emission. Subsequently, a pair of dendritic linkages was introduced to both sides of the fluorophore, to which six copies of monosaccharides (d-glucose, d-galactose or l-fucose) were introduced through azide-alkyne click chemistry. The resulting AIE-active glycoclusters were shown to be capable of (1) fluorogenic sensing of a diverse range of glycosidases including β-d-galactosidase, β-d-glucosidase and α-l-fucosidase through the AIE mechanism, (2) fluorescence imaging of the endogenous glycosidase activities in healthy and cancer cells, and during cell senescence, and (3) glycosidase-activated, long-term imaging of cells. The present study provides a general strategy to the functional, in situ imaging of glycosidase activities through the multivalent display of sugar epitopes of interest onto properly designed AIE-active fluorogens.We report a simple protocol for the transition metal-free, visible-light-driven conversion of 1,3-diketones to tetra-substituted furan skeleton compounds in carbon dioxide (CO2) atmosphere under mild conditions. It was found that CO2 could be incorporated at the diketone enolic OH position, which was key to enabling the cleavage of a C-O bond during the rearrangement of a cyclopropane intermediate. This method allows for the same-pot construction of two isomers of the high-value tetra-substituted furan scaffold. The synthetic scope and preliminary mechanistic investigations are presented.Chiral, substituted cyclobutanes are common motifs in bioactive compounds and intermediates in organic synthesis but few asymmetric routes for their synthesis are known. Herein we report the Rh-catalyzed asymmetric hydrometallation of a range of meso-cyclobutenes with salicylaldehydes. The ortho-phenolic group promotes hydroacylation and can be used as a handle for subsequent transformations. The reaction proceeds via asymmetric hydrometallation of the weakly activated cyclobutene, followed by a C-C bond forming reductive elimination. A prochiral, spirocyclic cyclobutene undergoes a highly regioselective hydroacylation. This report will likely inspire the development of other asymmetric addition reactions to cyclobutenes via hydrometallation pathways.Critical limiting factors in next generation electrode materials for rechargeable batteries include short lifetimes, poor reaction reversibility, and safety concerns. Many of these challenges are caused by detrimental interactions at the interfaces between electrode materials and the electrolyte. Thermally annealed polyacrylonitrile has recently shown empirical success in mitigating such detrimental interactions when used in conjunction with alloy anode materials, though the mechanisms by which it does so are not well understood. This is a common problem in the battery community an additive or a coating improves certain battery characteristics, but without a deeper understanding of how or why, design rules to further motivate the design of new chemistries can't be developed. Herein, we systematically investigate the effect of heating parameters on the properties of annealed polyacrylonitrile to identify the structural basis for such beneficial properties. We find that sufficiently long annealing times and control over temperature result in the formation of conjugated imine domains. When sufficiently large, the conjugated domains can be electrochemically reduced in a Li-ion half-cell battery, effectively n-doping the polymeric matrix and allowing it to become a mixed-conductor, with the ability to conduct both the Li-ions and electrons needed for reversible lithiation of an interdispersed alloy active material like antimony. Not only do those relationships inform design principles for annealed polyacrylonitrile containing electrodes, but they also identify new strategies in the development of mixed-conducting materials for use in next generation battery electrodes.The specific combination of human serum albumin and fluorescent dye will endow superior performance to a coupled fluorescent platform for in vivo fluorescence labeling. In this study, we found that lysine-161 in human serum albumin is a covalent binding site and could spontaneously bind a ketone skeleton quinoxaline-coumarin fluorescent dye with a specific turn-on fluorescence signal for the first time. Supported by the abundant drug binding domains in human serum albumin, drugs such as ibuprofen, warfarin and clopidogrel could interact with the fluorescent dye labeled human serum albumin to feature a substantial enhancement in fluorescence intensity (6.6-fold for ibuprofen, 4.5-fold for warfarin and 5-fold for clopidogrel). The drug concentration dependent fluorescence intensity amplification realized real-time, in situ blood drug concentration monitoring in mice, utilizing ibuprofen as a model drug. The non-invasive method avoided continuous blood sample collection, which fundamentally causes suffering and consumption of experimental animals in the study of pharmacokinetics. At the same time, the coupled fluorescent probe can be efficiently enriched in tumors in mice which could map a tumor with a high-contrast red fluorescence signal and could hold great potential in clinical tumor marking and surgical resection.We demonstrate phage-display screening on self-assembled ligands that enables the identification of oligopeptides that selectively bind dynamic supramolecular targets over their unassembled counterparts. The concept is demonstrated through panning of a phage-display oligopeptide library against supramolecular tyrosine-phosphate ligands using 9-fluorenylmethoxycarbonyl-phenylalanine-tyrosine-phosphate (Fmoc-FpY) micellar aggregates as targets. The 14 selected peptides showed no sequence consensus but were enriched in cationic and proline residues. The lead peptide, KVYFSIPWRVPM-NH2 (P7) was found to bind to the Fmoc-FpY ligand exclusively in its self-assembled state with K D = 74 ± 3 μM. Circular dichroism, NMR and molecular dynamics simulations revealed that the peptide interacts with Fmoc-FpY through the KVYF terminus and this binding event disrupts the assembled structure. In absence of the target micellar aggregate, P7 was further found to dynamically alternate between multiple conformations, with a preferred hairpin-like conformation that was shown to contribute to supramolecular ligand binding. Three identified phages presented appreciable binding, and two showed to catalyze the hydrolysis of a model para-nitro phenol phosphate substrate, with P7 demonstrating conformation-dependent activity with a modest k cat/K M = 4 ± 0.3 × 10-4 M-1 s-1.The scarcity of two-dimensional (2D) magnetic nanostructures has hindered their applications in spintronics, which is attributed to that most magnetic materials exhibit non-van der Waals (nvdWs) structures and it is hard to reduce their thickness to 2D nanostructures. Thus it is necessary to develop a promising strategy for free-standing 2D magnetic nvdWs nanostructures. We have achieved free-standing 2D nvdWs hexagonal FeSe with a thickness of 2.9 nm by the reaction between the oleylamine-Se complex and Fe2+ with the assistance of Cl-, where the synergetic effects of Cl- and -NH2 lead to anisotropic growth. Inspiringly, the 2D hexagonal FeSe exhibits intrinsic antiferromagnetic order rooted in Fe2+ and semiconducting nature. In addition, the temperature variation would result in the chemical environment changes of Fe2+, responsible for the temperature-dependent magnetic transitions. This work promotes the potential applications of 2D hexagonal FeSe and the preparation of other 2D nvdWs materials.Here, we used an unconventional idea of cooperative vibrational strong coupling of solute and solvent molecules to enhance the rate of an esterification reaction. Infigratinib FGFR inhibitor Different derivatives of p-nitrophenyl benzoate (solute) and isopropyl acetate (solvent) are cooperatively coupled to an infrared Fabry-Perot cavity mode. The apparent rates are increased by more than six times at the ON resonance condition, and the rate enhancement follows the lineshape of the vibrational envelope. Very interestingly, a strongly coupled system doesn't obey the Hammett relations. Thermodynamics suggests that the reaction mechanism remains intact for cavity and non-cavity conditions. Temperature-dependent experiments show an entropy-driven process for the coupled molecules. Vacuum field coupling decreases the free energy of activation by 2-5 kJ mol-1, supporting a catalysis process. The non-linear rate enhancement can be due to the reshuffling of the energy distribution between the substituents and the reaction center across the aromatic ring. These findings underline the non-equilibrium behavior of cavity catalysis.Thionyl fluoride (SOF2) was first isolated in 1896, but there have been less than 10 subsequent reports of its use as a reagent for organic synthesis. This is partly due to a lack of facile, lab-scale methods for its generation. Herein we report a novel protocol for the ex situ generation of SOF2 and subsequent demonstration of its ability to access both aliphatic and aromatic acyl fluorides in 55-98% isolated yields under mild conditions and short reaction times. We further demonstrate its aptitude in amino acid couplings, with a one-pot, column-free strategy that affords the corresponding dipeptides in 65-97% isolated yields with minimal to no epimerization. The broad scope allows for a wide range of protecting groups and both natural and unnatural amino acids. Finally, we demonstrated that this new method can be used in sequential liquid phase peptide synthesis (LPPS) to afford tri-, tetra-, penta-, and decapeptides in 14-88% yields without the need for column chromatography. We also demonstrated that this new method is amenable to solid phase peptide synthesis (SPPS), affording di- and pentapeptides in 80-98% yields.
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